US5807805A - Substituted thiophene derivatives as pesticides and herbicides - Google Patents

Substituted thiophene derivatives as pesticides and herbicides Download PDF

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US5807805A
US5807805A US08/836,336 US83633697A US5807805A US 5807805 A US5807805 A US 5807805A US 83633697 A US83633697 A US 83633697A US 5807805 A US5807805 A US 5807805A
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alkyl
alkoxy
optionally substituted
chlorine
sub
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Reiner Fischer
Jacques Dumas
Thomas Bretschneider
Bernd Gallenkamp
Folker Lieb
Konrad Wernthaler
Christoph Erdelen
Ulrike Wachendorff-Neumann
Norbert Mencke
Andreas Turberg
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Bayer AG
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Bayer AG
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Priority claimed from DE19527190A external-priority patent/DE19527190A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring

Definitions

  • the invention relates to novel thiophene derivatives, to a number of processes for their preparation and to their use as pesticides and herbicides.
  • Novel thiophene derivatives have now been found of the formula (I) ##STR3## in which X represents halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, nitro or cyano, or two substituents X together with the carbon atoms to which they are attached, form a saturated or unsaturated, optionally substituted ring,
  • n 1, 2 or 3
  • Z represents one of the groups ##STR4## in which A represents hydrogen, optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally substituted cycloalkyl which is optionally interrupted by at least one heteroatom, or represents aryl, arylalkyl, or hetaryl each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy or nitro,
  • B represents hydrogen, alkyl or alkoxyalkyl, or
  • a and B together with the carbon atom to which they are attached, represent a saturated or unsaturated, unsubstituted or substituted ring which is optionally ally interrupted by at least one heteroatom,
  • D represents hydrogen or optionally substituted radicals from the series consisting of alky, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl which is optionally interrupted by at least one heteroatom, arylalkyl, aryl, hetarylalkyl or hetaryl, or
  • a and D together with the atoms to which they are attached, represent a saturated or unsaturated, unsubstituted or substituted ring which is optionally interrupted by at least one heteroatom,
  • Q 1 , Q 2 and Q 3 independently of one another, represent hydrogen or optionally substituted alkyl, or
  • G represents hydrogen (a) or one of the groups ##STR5## in which E represents a metal ion equivalent or an ammonium ion,
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • R 1 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl which is optionally substituted by halogen, alkyl or alkoxy and may be interrupted by at least one heteroatom, or represents in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
  • R 2 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl,
  • R 3 , R 4 and R 5 independently of one another, represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and in each case optionally substituted phenyl, phenylalkyl, phenoxy or phenylthio,
  • R 6 and R 7 independently of one another, represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or represent, together with the nitrogen atom to which they are attached, a ring which is optionally interrupted by oxygen or sulfur.
  • the compounds of the formula (I) may themselves and in dependence on the nature of the substituents be present as geometrical and/or optical isomers or isomer mixtures, in varying composition, which can if desired be separated in a conventional manner. Both the pure isomers and the isomer mixtures, their preparation and use and compositions containing them are part of the claimed invention. However, for the sake of simplicity, the text below will always refer to compounds of the formula (I) although what are meant are both the pure compounds and, if appropriate, mixtures with different proportions of isomeric compounds.
  • the compounds of the formula (I-5) may, depending on the position of the substituent G, be present in the two isomeric forms of the formulae (I-5) a and (I-5) b ##STR12## which is what the dashed line in the formula (I-5) is intended to express.
  • the compounds of the formulae (I-5) a and (I-5) b may be present both as mixtures and in the form of their pure isomers. Mixtures of compounds of the formulae (I-5) a and (I- 5 ) b can if desired be separated by physical methods in a manner known per se, for example by chromatographic methods.
  • the compounds of the formula (I-7) may, depending on the position of the substituent G, be present in the two isomeric forms of the formulae (I-7) a and (I-7) b ##STR15## which is what the dashed line in the formula (I-7) is intended to express.
  • the compounds of the formulae (I-7) a and (I- 7 ) b may be present both as mixtures and in the form of their pure isomers. Mixtures of compounds of the formulae (I-7) a and (I- 7 ) b ) can if desired be separated by physical methods in a manner known per se, for example by chromatographic methods.
  • the compounds of the formula (I-8) may, depending on the position of the substituent G, be present in the two isomeric forms of the formulae (I-8) a and (I-8) b ##STR17## which is what the dashed line in the formula (I-8) is intended to express.
  • the compounds of the formulae (I-8) a and (I-8) b may be present both as mixtures and in the form of their pure isomers. Mixtures of compounds of the formula (I-8) a and (I- 8 ) b ) can if desired be separated by physical methods in a manner known per se, for example by chromatographic methods.
  • R 8 represents alkyl, preferably C 1 -C 6 -alkyl, to intramolecular condensation in the presence of a diluent and in the presence of a base.
  • W represents hydrogen, halogen, alkyl, preferably C 1 -C 6 -alkyl, or alkoxy, preferably C 1 -C 8 -alkoxy,
  • Hal represents halogen, especially chlorine or bromine or
  • a and D have the meanings given above, if desired in the presence of a diluent and if desired in the presence of a base.
  • Hal represents halogen, preferably chlorine or bromine, if desired in the presence of a diluent and if desired in the presence of an acid acceptor.
  • Hal represents halogen, especially chlorine or bromine, or
  • R 1 has the meaning given above
  • R 2 and M have the meanings given above, if desired in the presence of a diluent and if desired in the presence of an acid-binding agent;
  • R 2 has the meaning given above, and
  • Hal represents chlorine, bromine or iodine
  • R 3 has the meaning given above
  • Hal represents halogen, especially chlorine or bromine
  • t represents the number 1 or 2
  • R 10 , R 11 and R 12 independently of one another, represent hydrogen or alkyl, preferably C 1 -C 8 -alkyl,
  • R 6 and L have the meanings given above
  • novel substituted thiophene derivatives of the formula (I) have a very good activity as pesticides, preferably as insecticides, acaricides, nematicides and herbicides, and as ectoparasiticides.
  • X preferably represents halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -halogenoalkyl, C 1 -C 6 -halogenoalkoxy, nitro or cyano or two substituents X, together with the carbon atoms to which they are attached, form a saturated or unsaturated 5- to 8-membered carbocyclic ring which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -halogenoalkyl, C 1 -C 6 -halogenoalkoxy, nitro or cyano.
  • n preferably represents 1, 2 or 3.
  • Z preferably represents one of the groups ##STR43##
  • A preferably represents hydrogen or in each case optionally halogen-substituted C 1 -C 12 -alkyl, C 2 -C 8 -alkenyl, C 1 -C 10 -alkoxy-C 1 -C 8 -alkyl, poly-C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 10 -alkylthio-C 1 -C 6 -alkyl, cycloalkyl having 3 to 8 ring atoms which is optionally substituted by C 1 -C 6 -alkyl, halogen or C 1 -C 6 -alkoxy and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur, or represents C 6 - or C 10 -aryl, hetaryl having 5 or 6 ring atoms and one to three heteroatoms from the series consisting of nitrogen, oxygen and sulfur, or C 6 - or C 10
  • B preferably represents hydrogen, C 1 -C 12 -alkyl or C 1 -C 8 -alkoxy-C 1 -C 6 -alkyl, or
  • A, B and the carbon atom to which they are attached preferably represent a saturated or unsaturated C 3 -C 10 spirocyclic system in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur and which is optionally substituted by C 1 -C 8 -alkyl, C 3 -C 10 -cycloalkyl, C 1 -C 8 -halogenoalkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, halogen or phenyl, or
  • A, B and the carbon atom to which they are attached preferably represent a C 3 -C 6 spirocyclic ring system which is substituted by an alkylenediyl group, optionally interrupted by one or two oxygen and/or sulfur atoms, or is substituted by an alkylenedioxy or by an alkylenedithio group, which, with the carbon atom to which it is attached, forms a further five- to eight-membered spirocyclic ring system, or
  • A, B and the carbon atom to which they are attached preferably represent a C 3 -C 8 spirocyclic ring system in which two substituents together represent a saturated or mono- or polyunsaturated 5- to 8-membered ring which is optionally substituted by C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or halogen and which optionally contains an oxygen or sulfur atom.
  • D preferably represents hydrogen, in each case optionally halogen-substituted C 1 -C 2 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkinyl, C 1 -C 10 -alkoxy-C 2 -C 8 -alkyl, poly-C 1 -C 8 -alkoxy-C 2 -C 8 -alkyl, C 1 -C 10 -alkylthio-C 2 -C 8 -alkyl, cycloalkyl having 3 to 8 ring atoms which is optionally substituted by hate-en, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkyl and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur, or represents phenyl, hetaryl having 5 or 6 ring atoms and one to three heteroatoms
  • a and D preferably represent, together with the atoms to which they are attached, an alkanediyl or alkenediyl grouping of 3 to 6 carbon atoms which is optionally substituted from one to four times by identical or different substituents, in which a) optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur, and suitable substituents being:
  • halogen hydroxyl, mercapto or in each case optionally halogen-substituted C 1 -C 10 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 3 -C 7 -cycloalkyl, phenyl or benzyloxy;
  • Q 1 , Q 2 and Q 3 independently of one another, preferably represent hydrogen or optionally halogen-substituted C 1 -C 6 -alkyl, or
  • B and Q 1 together preferably represent a C 1 -C 6 -alkanediyl grouping which is optionally substituted by halogen or C 1 -C 6 -alkyl.
  • G preferably represents hydrogen (a) or represents one of the groups ##STR45## in which E represents a metal ion equivalent or an ammonium ion,
  • L represents oxygen or sulfur
  • M oxygen or sulfur.
  • R 1 preferably represents in each case optionally halogen-substituted C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, C 1 -C 8 -alkylthio-C 1 -C 8 -alkyl, poly-C 1 -C 5 -alkoxy-C 1 -C 8 -alkyl, or represents cycloalkyl having 3 to 8 ring atoms which is optionally substituted by halogen or C 1 -C 6 -alkyl and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur,
  • phenyl which is optionally substituted by halogen, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -halogenoalkyl, C 1 -C 6 -halogenoalkoxy, C 1 -C 6 -alkylthio or C 1 -C 6 -alkylsulfonyl,
  • phenyl-C 1 -C 6 -alkyl which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -halogenoalkyl or C 1 -C 6 -haloogenoalkoxy,
  • R 2 preferably represents in each case optionally halogen-substituted C 1 -C 20 -alkyl, C 3 -C 20 -alkenyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl or poly-C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl,
  • R 3 preferably represents optionally halogen-substituted C 1 -C 8 -alkyl or represents benzyl or phenyl each of which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 3 -halogenoalkyl, C 1 -C 3 -halogenoalkoxy, nitro or cyano.
  • R 4 and R 5 preferably represent, independently of one another, optionally halogen-substituted C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylamino, di-(C 1 -C 8 -alkyl)amino, C 1 -C 8 -alkylthio, C 2 -C 8 -alkenylthio, C 3 -C 7 -cycloalkylthio, or represent phenyl, phenoxy or phenylthio each of which is optionally substituted by halogen, nitro, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -halegenoalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -halogenoalkylthio, C 1 -C 4 -alkyl or C 1 -C 4 -halogenoalkyl.
  • R 6 and R 7 independently of one another, preferably represent hydrogen, in each case optionally halogen-substituted C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 8 -alkoxy, C 3 -C 8 -alkenyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, phenyl which is optionally substituted by halogen, C 1 -C 8 -halogenoalkyl, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy, benzyl which is optionally substituted by halogen, C 1 -C 8 -alkyl, C 1 -C 8 -halogenoalkyl or C 1 -C 8 -alkoxy, or together represent C 3 -C 6 -alkanediyl in which, optionally, one methylene group is replaced by oxygen or sulfur.
  • R 13 preferably represents hydrogen, in each case optionally halogen-substituted C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy or C 3 -C 8 -cycloalkyl, or represents phenyl or benzyl each of which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 3 -halogenoalkyl, C 1 -C 3 -halogenoalkoxy, nitro or cyano.
  • R 14 and R 15 preferably represent, independently of one another, hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -halogenoalkyl, C 3 -C 6 -cycloalkyl, or represent phenyl or benzyl each of which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 3 -halogenoalkyl, C 1 -C 3 -halogenoalkoxy, cyano or nitro, or together represent an optionally C 1 -C 4 -alkyl-substituted C 4 -C 6 -alkanediyl group.
  • R 16 and R 17 are identical or different and preferably represent C 1 -C 6 -alkyl, or
  • R 16 and R 17 together preferably represent a C 2 -C 4 -alkanediyl radical which is optionally substituted by C 1 -C 6 -alkyl or by phenyl which is optionally substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy, nitro or cyano.
  • R 18 and R 19 independently of one another, preferably represent hydrogen, optionally halogen-substituted C 1 -C 8 -alkyl, or phenyl which is optionally substituted by halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -halogenoalkoxy, nitro or cyano.
  • R 20 and R 21 independently of one another, preferably represent C 1 -C 10 -alkyl, C 3 -C 10 -alkenyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylamino, C 3 -C 10 -alkenylamino, di-(C 1 -C 10 -alkyl)-amino or di-(C 3 -C 10 -alkenyl)-amino.
  • X particularly preferably represents fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -halogenoalkoxy, nitro or cyano
  • substituents X form, together with the carbon atoms to which they are attached, an unsaturated 5- to 7-membered carbocyclic ring which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -halogenoalkoxy, nitro or cyano.
  • n particularly preferably represents 1, 2 or 3.
  • Z particularly preferably represents one of the groups ##STR46##
  • B particularly preferably represents hydrogen, C 1 -C 10 -alkyl or C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, or
  • A, B and the carbon atom to which they are attached particularly preferably represent a saturated or unsaturated C 3 -C 9 spirocyclic ring system in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur and which is optionally substituted by C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 3 -halogenoalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, fluorine, chlorine or phenyl, or
  • A, B and the carbon atom to which they are attached particularly preferably represent a C 3 -C 6 spirocyclic ring system which is substituted by an alkylenediyl group, which is optionally interrupted by one or two oxygen or sulfur atoms or by an alkylenedioxy group or by an alkylenedithio group, which, with the carbon atom to which it is attached, forms a further five- to seven-membered spirocyclic ring system, or
  • A, B and the carbon atom to which they are attached particularly preferably represent a C 3 -C 6 spirocyclic ring system in which two substituents together represent a saturated or mono- or polyunsaturated 5- or 6-membered ring, which is optionally substituted by C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy, fluorine, chlorine or bromine and which optionally contains an oxygen or sulfur atom.
  • D particularly preferably represents hydrogen, in each case optionally, fluorine- or chlorine-substituted C 1 -C 10 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkinyl, C 1 -C 8 -alkoxy-C 2 -C 6 -alkyl, poly-C 1 -C 6 -alkoxy-C 2 -C 6 -alkyl, C 1 -C 8 -alkylthio-C 2 -C 6 -alkyl, cycloalkyl having 3 to 7 ring atoms which is optionally substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 2 -halogenoalkyl and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur, or represents phenyl, pyridyl, thienyl, furanyl, thiazo
  • a and D particularly preferably represent, together with the atoms to which they are attached, a C 3 -C 5 -alkanediyl or C 3 -C 5 -alkenediyl grouping
  • a) optionally, one methylene group is replaced by oxygen or sulfur and which is optionally substituted by fluorine, chlorine, hydroxyl or mercapto or by in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 -cycloalkyl, phenyl or benzyl;
  • B and Q 1 particularly preferably represent a C 1 -C 4 -alkanediyl grouping which is optionally substituted by fluorine, chlorine or C 1 -C 4 -alkyl.
  • G particularly preferably represents hydrogen (a) or represents one of the groups ##STR49## in which E represents a metal ion equivalent or an ammonium ion,
  • L represents oxygen or sulfur
  • M oxygen or sulfur.
  • R 1 particularly preferably represents in each case optionally fluorine- or chlorine-substituted C 1 -C 16 -alkyl, C 2 -C 16 -alkenyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylthio-C 1 -C 6 -alkyl, poly-C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, or cycloalkyl having 3 to 7 ring atoms which is optionally substituted by fluorine, chlorine or C 1 -C 5 -alkyl and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur,
  • phenyl-C 1 -C 4 -alkyl which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 3 -halogenoalkyl or C 1 -C 3 -halogenoalkoxy,
  • pyrazolyl or represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally substituted by fluorine, chlorine, bromine or C 1 -C 4 -alkyl,
  • pyridyloxy-C 1 -C 5 -alkyl represents pyridyloxy-C 1 -C 5 -alkyl, pyrimidyloxy-C 1 -C 5 -alkyl or thiazolyloxy-C 1 -C 5 -alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, amino or C 1 -C 4 -alkyl.
  • R 2 particularly preferably represents in each case optionally fluorine- or chlorine-substituted C 1 -C 16 -alkyl, C 3 -C 16 -alkenyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl or poly-C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl,
  • R 3 particularly preferably represents optionally fluorine- or chlorine-substituted C 1 -C 6 -alkyl or represents benzyl or phenyl each of which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 2 -halogenoalkyl, C 1 -C 2 -halogenoalkoxy, nitro or cyano.
  • R 4 and R 5 particularly preferably represent, independently of one another, in each case optionally halogen-substituted C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkyl-amino, di-(C 1 -C 6 -alkyl)-amino, C 1 -C 6 -alkylthio, C 3 -C 4 -alkenylthio, C 3 -C 6 -cycloalkylthio, or represent phenyl, phenoxy or phenylthio each of which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C 1 -C 3 -alkoxy, C 1 -C 3 -halogeno-alkoxy, C 1 -C 3 -alkylthio, C 1 -C 3 -halogenoalkylthio, C 1 -C 3 -alkyl or C 1 -C 3
  • R 6 and R 7 independently of one another, particularly preferably represent hydrogen, in each case optionally fluorine-, chlorine- or bromine-substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, phenyl which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 5 -halogenoalkyl, C 1 -C 5 -alkyl or C 1 -C 5 -alkoxy, benzyl which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 5 -alkyl, C 1 -C 5 -halogenoalkyl or C 1 -C 5 -alkoxy, or together represent C 3 -C 6 -alkanediyl in which, optionally flu
  • R 13 particularly preferably represents hydrogen, in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or C 1 -C 7 -cycloalkyl, or represents phenyl or benzyl each of which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 2 -halogenoalkyl, C 1 -C 2 -halogenoalkoxy, nitro or cyano.
  • R 14 and R 15 particularly preferably represent, independently of one another, hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -halogenoalkyl, C 3 -C 6 -cycloalkyl, or represent phenyl or benzyl each of which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 2 -halogenoalkyl, C 1 -C 2 -halogenoalkoxy, cyano or nitro, or together represent an optionally C 1 -C 3 -alkyl-substituted C 4 -C 5 -alkanediyl group.
  • R 16 and R 17 are identical or different and particularly preferably represent C 1 -C 4 -alkyl, or
  • R 16 and R 17 together particularly preferably, represent a C 2 -C 3 -alkanediyl radical which is optionally substituted by C 1 -C 4 -alkyl or by phenyl which is optionally substituted by C 1 -C 2 -alkyl, C 1 -C 2 -halogenoalkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -halogenoalkoxy, nitro or cyano.
  • X very particularly preferably represents flourine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, trifluoromethoxy, nitro or cyano
  • substituents X form, together with the carbon atoms to which they are attached, an unsaturated 6-membered carbocyclic ring which is optionally substituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
  • n very particularly preferably represents 1, 2 or 3.
  • Z very particularly preferably represents one of the groups ##STR50##
  • B very particularly preferably represents hydrogen, C 1 -C 8 -alkyl or C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl, or
  • A, B and the carbon atom to which they are attached very particularly preferably represent a saturated or unsaturated C 3 -C 8 spirocyclic ring system in which, optionally, one methylene group is replaced by oxygen or sulfur, and which is optionally mono-or poly-substituted by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl, or
  • A, B and the carbon atom to which they are attached very particularly preferably represent a C 3 -C 6 spirocyclic ring system which is substituted by an alkylenediyl group, which is optionally interrupted by an oxygen or sulfur atom or by an alkylenedioxy group which, with the carbon atom to which it is attached, forms a further five- to seven-membered spirocyclic ring system, or
  • A, B and the carbon atom to which they are attached very particularly preferably represent a C 3 -C 6 spirocyclic ring system in which two substituents together represent a saturated or mono- to triunsaturated five- or six-membered ring which optionally contains an oxygen or sulfur atom.
  • D very particularly preferably represents hydrogen, in each case optionally fluorine- or chlorine-substituted C 1 -C 8 -alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkinyl, C 1 -C 6 -alkoxy-C 2 -C 4 -alkyl, poly-C 1 -C 4 -alkoxy-C 2 -C 4 -alkyl, C 1 -C 4 -alkylthio-C 2 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, in which, optionally, one methylene group is replaced by oxygen or sulfur, or represents phenyl, benzyl, pyridyl, thienyl, furanyl or thiazolyl each of which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluor
  • a and D very particularly preferably represent, together with the atoms to which they are attached, a C 3 -C 5 -alkanediyl or C 3 -C 5 -alkenediyl groupings in which, optionally, one methylene group is replaced by oxygen or sulfur and which is optionally substituted by fluorine, chlorine, hydroxyl or mercapto or by in each case optionally fluorine- or chlorine-substituted C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 -cycloalkyl, phenyl or benzyloxy,
  • B and Q 1 together very particularly preferably represent a C 1 -C 4 -alkanediyl grouping which is optionally substituted by fluorine, chlorine methyl or ethyl.
  • G very particularly preferably represents hydrogen (a) or represents one of the groups ##STR52## in which E represents a metal ion equivalent or an ammonium ion,
  • L represents oxygen or sulfur
  • M oxygen or sulfur.
  • R 1 very particularly preferably represents in each case optionally fluorine- or chlorine-substituted C 1 -C 14 -alkyl, C 2 -C 14 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 4 -alkylthio-C 1 -C 6 -alkyl, poly-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl or C 3 -C 6 -cycloalkyl which is optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl and in which, optionally, one or two methylene groups which are not directly adjacent are replaced by oxygen and/or sulfur,
  • phenyl which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl or nitro,
  • benzyl which is optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoroethyl or trifluoromethoxy,
  • phenoxy-C 1 -C 4 -alkyl which is optionally substituted by fluorine, chlorine, methyl or ethyl, or represents pyridyloxy-C 1 -C 4 -alkyl, pyrimidyloxy-C 1 -C 4 -alkyl or thiazolyloxy-C 1 -C 4 -alkyl, each of which is optionally substituted by fluorine, chlorine, amino, methyl or ethyl.
  • R 2 very particularly preferably represents in each case optionally fluorine- or chlorine-substituted C 1 -C 14 -alkyl, C 3 -C 14 -alkenyl, C 1 -C 14 -alkoxy-C 1 -C 6 -alkyl or poly-C 1 -C 4 -alkoxy-C 1 -C 6 -alkyl,
  • R 3 very particularly preferably represents optionally fluorine- or chlorine-substituted C 1 -C 4 -alkyl or represents phenyl or benzyl each of which is optionally substituted by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy, nitro or cyano.
  • R 4 and R 5 very particularly preferably represent, independently of one another, in each case optionally fluorine- or chlorine-substituted C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylamino, di-(C 1 -C 4 -alkyl)-amino, C 1 -C 4 -alkylthio or represent phenyl, phenoxy or phenylthio each of which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C 1 -C 2 -alkoxy, C 1 -C 2 -fluoroalkoxy, C 1 -C 2 -alkylthio, C 1 -C 2 -fluoroalkylthio or C 1 -C 3 -alkyl.
  • R 6 and R 7 independently of one another, very particularly preferably represent hydrogen, in each case optionally fluorine-, chlorine- or bromine-substituted C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 3 -C 4 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl which is optionally substituted by fluorine, chlorine, bromine, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, or represents benzyl which is optionally substituted by fluorine, chlorine, bromine C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl or C 1 -C 4 -alkoxy, or together represent C 4 -C 6 -alkanediyl in which,
  • radicals X may be identical or different.
  • radicals given above may be combined at will with one another, which thus includes combinations between the respective ranges and ranges of preference. They apply correspondingly to the end products and to the precursors and intermediates.
  • Saturated or unsaturated hydrocarbon radicals may where possible alone or in conjunction with heteroatoms such as, for example, in alkoxy, each be straight-chain or branched.
  • Hal represents chlorine or bromine
  • the compounds of the formula (XXV) are obtained by acylating amino acids of the formula (XXVI) ##STR77## in which A, B and D have the meanings given above with thienylacetyl halides of the formula (XXIV) ##STR78## in which X and n have the meanings given above and
  • Hal represents chlorine or bromine
  • the compounds of the formula (XXIV) are in some cases known or can be prepared by known methods.
  • the substituted cyclic aminocarboxylic acids of the formula (XXVIa) in which A and B form a ring are in general obtainable by the Bucherer-Bergs synthesis or by the Strecker synthesis, in each of which syntheses they are produced in different isomeric forms.
  • the isomers obtained under the conditions of the Bucherer-Bergs synthesis are predominantly those (referred to for simplicity below as ⁇ ) in which the radicals R and the carboxyl group are in equatorial positions
  • the isomers obtained under the conditions of the Strecker synthesis are predominantly those (referred to for simplicity below as ⁇ ) in which the amino group and the radicals R are in equatorial positions.
  • the starting materials used in the above process (A), of the formula (II) ##STR80## in which A, B, D, X, n and R 8 have the meanings given above can be prepared by reacting amino nitriles of the formula (XXVII) ##STR81## in which A, B and D have the meanings given above with thienylacetyl halides of the formula (XXIV) ##STR82## in which X and n have the meanings given above, and
  • Hal represents chlorine or bromine
  • the compounds of the formula (III) are obtained by acylating 2-hydroxycarboxylic esters of the formula (XXIX) ##STR85## in which A, B and R 8 have the meanings given above with thienylacetyl halides of the formula (XXIV) ##STR86## in which X and n have the meanings given above and
  • Hal represents chlorine or bromine
  • Hal represents chlorine or bromine.
  • the compounds of the formulae (XXX) and (XXXI) are generally known compounds and/or can be prepared in a simple manner by known methods.
  • the compounds of the formula (IV) are obtained by acylating thienylacetic esters of the formula (XXXII) ##STR90## in which X, R 8 and n have the meanings given above with 2-benzylthio-carbonyl halides of the formula (XXIII) ##STR91## in which A, B and W have the meanings given above, and
  • Hal represents halogen, especially chlorine or bromine
  • benzylthio-carbonyl halides of the formula (XXXIII) are in some cases known and/or can be prepared by known methods (J. Antibiotics (1983), 26, 1589).
  • halogenocarbonyl ketenes required as starting materials in the above process (D ⁇ ), of the formula (V), are novel. They can be prepared in a simple manner by methods which are known in principle (cf. for example Org. Prep. Proced. Int., 7, (4), 155-158, 1975 and DE 1 945 703).
  • compounds of the formula (V) ##STR92## in which X and n have the meanings given above, and
  • Hal represents chlorine or bromine
  • thienylmalonic acids of the formula (XXXIV) ##STR93## in which X and n have the meanings given above with acid halides such as, for example, thionyl chloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalyl chloride, phosgene or thionyl bromide, if desired in the presence of catalysts such as, for example, diethylformamide, methylstearylformamide or triphenylphosphine and if desired in the presence of bases such as, for example, pyridine or triethylamine.
  • acid halides such as, for example, thionyl chloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalyl chloride, phosgene or thionyl bromide, if desired in the presence of catalysts such as, for example, diethylformamide, methylstearylformamide or triphen
  • thienylmalonic acids of the formula (XXXIV) are in some cases known compounds of organic chemistry and can be prepared in a simple manner by known methods (cf. e.g. Organikum, VEB Deutscher Verlag dermaschineen, Berlin 1977, p. 517 ff.).
  • the compounds of the formula (XXXV) are obtained by reacting carboxylic anhydrides of the formula (XXXVI) ##STR100## in which A, B, D and Q 1 have the meanings given above with organometallic compounds of the formula (XXXVII) ##STR101## in which X and n have the meanings given above,
  • Me mono- or divalent metal ions such as, for example, lithium or magnesium
  • Hal represents chlorine or bromine
  • the compounds (XXXVI) and (XXXVII) are in some cases known and/or can be prepared in a simple manner by known methods (cf. e.g. Organikum, 15th edition, Berlin, 1977, pages 525, 526 and 623).
  • 5-thienyl-4-ketocarboxylic acids of the formula (XXXV) ##STR102## in which A, B, D, Q 1 , X and n have the meanings given above are obtained by subjecting 2-thienyl-3-oxo-adipic esters of the formula (XXXVIII) ##STR103## in which A, B, D, Q 1 , X and n have the meanings given above, and
  • R 8 and R 8' are identical or different and represent alkyl, preferably C 1 -C 6 -alkyl,
  • the compounds of the formulae (XXXII) and (XXXIX) are generally known compounds of organic chemistry and/or can be prepared in a simple manner by methods which are known in principle.
  • the compounds of the formula (XL) are obtained by reacting carboxylic anhydrides of the formula (XLI) ##STR110## in which A, B, D, Q 1 , Q 2 and Q 3 have the meanings given above with organometallic compounds of the formula (XXXVII) ##STR111## in which X and n have the meanings given above,
  • Me mono- or divalent metal ions such as, for example, lithium and magnesium
  • Hal represents chlorine or bromine
  • the compounds (XXXVII) and (XLI) are in some cases known and/or can be prepared in a simple manner by known methods (cf. e.g. Organikum, 15th edition, Berlin, 1977, pages 525, 526 and 623).
  • 6-thienyl-5-ketocarboxylic acids of the formula (XL) ##STR112## in which A, B, D, Q 1 , Q 2 , Q 3 , X and n have the meanings given above are obtained by subjecting 2-thienyl-3-oxo-heptanedioic esters of the formula (XLII) ##STR113## in which A, B, D, Q 1 , Q 2 , Q 3 , X, R 8 , R 8' and n have the meanings given above to hydrolysis and decarboxylation, if desired in the presence of a diluent and if desired in the presence of a base or acid (cf. e.g. Organikum, 15th edition, Berlin, 1977, page 519 to 521).
  • Hal represents chlorine or bromine
  • the compounds of the formulae (XXXII) and (XLIII) are generally known compounds of organic chemistry and/or can be prepared in a simple manner by methods which are known in principle (cf. e.g. EP-A-0 307 103).
  • Process (A) comprises subjecting compounds of the formula (II) in which A, B, D, X, n and R 8 have the meanings given above to an intramolecular condensation in the presence of bases.
  • inert organic solvents As diluents in process (A) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • bases (deprotonating agents) for carrying out process (A) according to the invention it is possible to employ all conventional proton acceptors.
  • alkali metals such as sodium or potassium.
  • Compounds which can also be employed are alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butylate.
  • reaction temperatures when carrying out process (A) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures of between 0° C. and 250° C., preferably between 50° C. and 150° C.
  • Process (A) according to the invention is generally carried out under atmospheric pressure.
  • reaction components of the formula (II) and the deprotonating bases are generally employed in approximately twice the equimolar quantity. However, it is also possible to use one or other component in a relatively large excess (up to 3 mol).
  • Process (B) comprises subjecting compounds of the formula (III) in which A, B, X, n and R 8 have the meanings given above to an intramolecular condensation in the presence of a base and of a diluent.
  • inert organic solvents As diluents in process (B) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • bases (deprotonating agents) for carrying out process (B) according to the invention it is possible to employ all conventional proton acceptors.
  • alkali metals such as sodium or potassium.
  • Compounds which can also be employed are alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butylate.
  • reaction temperatures when carrying out process (B) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures of between 0° C. and 250° C., preferably between 50° C. and 150° C.
  • Process (B) according to the invention is generally carried out under atmospheric pressure.
  • reaction components of the formula (III) and the deprotonating bases are generally employed in approximately twice the equimolar quantity. However, it is also possible to use one or other component in a relatively large excess (up to 3 mol).
  • Process (C) comprises subjecting compounds of the formula (IV) in which A, B, W, X, n and R 8 have the meanings given above to an intramolecular cyclization in the presence of acids and if desired in the presence of a diluent.
  • inert organic solvents As diluents in process (C) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, ethylene chloride, chlorobenzene and dichlorobenzene, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • the acid employed can also be used as diluent.
  • acids in process (C) according to the invention it is possible to employ all customary inorganic and organic acids, for example hydrohalic acids, sulfuric acid, alkyl-, aryl- and haloalkylsulfonic acids, and, in particular, halogenated alkylcarboxylic acids such as trifluoroacetic acid.
  • hydrohalic acids sulfuric acid, alkyl-, aryl- and haloalkylsulfonic acids
  • halogenated alkylcarboxylic acids such as trifluoroacetic acid.
  • reaction temperatures when carrying out process (C) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures between 0° C. and 250° C., preferably between 50° C. and 150° C.
  • Process (C) according to the invention is generally carried out under atmospheric pressure.
  • reaction components of the formula (IV) and the acid are employed, for example, in equimolar amounts. It is also possible, if desired, to use the acid as solvent or as catalyst.
  • the processes (D- ⁇ ) and (D- ⁇ ) comprise subjecting compounds of the formulae (V) or (VI) in which X, R 8 , n and Hal have the meanings given above, and compounds of the formula (VII) in which A and D have the meanings given above, to a condensation reaction, if desired in the presence of a base and if desired in the presence of a diluent.
  • inert organic solvents As diluents in processes (D- ⁇ ) and (D- ⁇ ) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • bases (deprotonating agents) for carrying out process (D- ⁇ ) and (D- ⁇ ) according to the invention it is possible to employ all conventional proton acceptors.
  • alkali metals such as sodium or potassium.
  • alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride
  • alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tert-butylate.
  • reaction temperatures when carrying out process (D- ⁇ ) and (D- ⁇ ) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures of between -20° C. and 250° C., preferably between 0° C. and 150° C.
  • Processes (D- ⁇ ) and (D- ⁇ ) according to the invention are generally carried out under atmospheric pressure.
  • reaction components of the formulae (V) and (VII) or (VI) and (VII) and the deprotonating bases which are employed if desired are in general employed in approximately equimolar amounts. However, it is also possible to use one or other component in a relatively large excess (up to 3 mol).
  • Process (E) comprises reacting carbonyl compounds of the formula (VIII) with ketene acid halides of the formula (II) in the presence of a diluent and if desired in the presence of an acid acceptor.
  • Diluents which can be employed in this context are all inert organic solvents.
  • Preferred possibilites for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Huinig base and N,N-dimethylaniline.
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • DBN diazabicyclononene
  • Huinig base and N,N-dimethylaniline.
  • reaction temperatures when carrying out process (E) according to the invention can be varied within a relatively large range. It is expediently carried out at temperatures of between 0° C. and 250° C., preferably between 50° C. and 220° C.
  • Process (E) is expediently carried out under atmospheric pressure.
  • reaction components of the formulae (VIII) and (V) in which A, D, X and n have the meanings given above and Hal represents halogen, and, if desired, the acid acceptors, are expediently employed in approximately equimolar amounts.
  • one or other component in a relatively large excess (up to 5 mol).
  • Process (F) comprises reacting thioamides of the formula (IX) with ketene acid halides of the formula (V), if desired in the presence of a diluent and if desired in the presence of an acid acceptor.
  • inert organic solvents As diluents in process (F) it is possible to employ all inert organic solvents. Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • hydrocarbons such as toluene and xylene
  • ethers such as dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • tertiary amines such as triethylamine, pyrridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Huinig base and N,N-dimethyl-aniline.
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • DBN diazabicyclononene
  • Huinig base and N,N-dimethyl-aniline.
  • the reaction temperatures can be varied within a relatively large range.
  • the process is expediently carried out at temperatures of between 0° C. and 250° C., preferably between 20° C. and 220° C.
  • Process (F) is expediently carried out under atmospheric pressure.
  • reaction components of the formulae (IX) and (V) in which A, X and n have the meanings given above and Hal represents halogen, and, if desired, the acid acceptors, are expediently employed in approximately equimolar amounts.
  • one or other component in a relatively large excess (up to 5 mol).
  • Process (G) comprises subjecting compounds of the formula (X) in which A, B, D, Q 1 , X, n and R 8 have the meanings given above to an intramolecular condensation in the presence of a base and if desired in the presence of a diluent.
  • inert organic solvents As diluents in process (G) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • bases (deprotonating agents) for carrying out process (G) according to the invention it is possible to employ all conventional proton acceptors.
  • Preferred possibilities for use are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be employed in the presence of phase transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (methyltrialkyl(C 8 -C 10 )ammonium chloride) or TDA 1 (tris-(methoxyethoxyethyl)-amine).
  • phase transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (methyltrialkyl(C 8 -C 10 )ammonium chloride) or TDA
  • alkali metals such as sodium or potassium.
  • Compounds which can also be employed are alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butylate.
  • reaction temperatures when carrying out process (G) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures of between 0° C. and 250° C., preferably between 50° C. and 150° C.
  • Process (G) according to the invention is generally carried out under atmospheric pressure.
  • reaction components of the formula (X) and the deprotonating bases are generally employed in approximately equimolar amounts. However, it is also possible to use one or other component in a relatively large excess (up to 3 mol).
  • Process (H) comprises subjecting compounds of the formula (XI) in which A, B, D, Q 1 , Q 2 , Q 3 , X, n and R 8 have the meanings given above to an intramolecular condensation in the presence of a base and if desired in the presence of a diluent.
  • inert organic solvents As diluents in process (H) according to the invention it is possible to employ all inert organic solvents.
  • Preferred possibilities for use are hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • bases (deprotonating agents) for carrying out process (H) according to the invention it is possible to employ all conventional proton acceptors.
  • Preferred possibilities for use are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be employed in the presence of phase transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (methyltrialkyl(C 8 -C 10 )ammonium chloride) or TDA 1 (tris-(methoxyethoxyethyl)-amine).
  • phase transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (methyltrialkyl(C 8 -C 10 )ammonium chloride) or TDA
  • alkali metals such as sodium or potassium.
  • Compounds which can also be employed are alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butylate.
  • reaction temperatures when carrying out process (H) according to the invention can be varied within a relatively large range. It is in general carried out at temperatures of between 0° C. and 250° C., preferably between 50° C. and 150° C.
  • Process (H) according to the invention is generally carried out under atmospheric pressure.
  • reaction components of the formula (XI) and the deprotonating bases are generally employed in approximately equimolar amounts. However, it is also possible to use one or other component in a relatively large excess (up to 3 mol).
  • Process (I ⁇ ) comprises reacting compounds of the formulae (I-1-a) to (I-8-a), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent, with carbonyl halides of the formula (XII).
  • diluents in process (I ⁇ ) it is possible to employ all solvents which are inert with respect to the acyl halides.
  • Preferred possibilities for use are hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ketones such as acetone and methyl isopropyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate, and strongly polar solvents such as dimethyl sulfoxide and sulfolane. If the stability of the acyl halide to hydrolysis permits, the reaction can also be carried out in the presence of water.
  • Suitable acid-binding agents in the reaction according to the process (I ⁇ ) according to the invention are all customary acid receptors.
  • Preferred possibilities for use are tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base and N,N-dimethyl-aniline, alkaline earth metal oxides such as magnesium oxide and calcium oxide, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • DABCO diazabicyclooctane
  • DBU diazabicycloundecene
  • DBN diazabicyclononene
  • Hunig base and N,N-dimethyl-aniline alkaline earth metal oxides such as magnesium oxide and calcium oxide
  • reaction temperatures when carrying out process (I ⁇ ) according to the invention can also be varied within a relatively large range. It is in general carried out at temperatures between -20° C. and +150° C., preferably between 0° C. and 100° C.
  • the starting materials of the formulae (I-1-a) to (I-8-a) and the carbonyl halide of the formula (XII) are generally employed in approximately equivalent amounts.
  • Process (I ⁇ ) comprises reacting compounds of the formulae (I-1-a) to (I-8-a), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent, with carboxylic anhydrides of the formula (XIII).
  • diluents in process (I ⁇ ) according to the invention it is possible preferably to use those diluents which are also preferably suitable when acyl halides are used.
  • a carboxylic anhydride employed in excess it is also possible for a carboxylic anhydride employed in excess to function simultaneously as diluent.
  • reaction temperatures when carrying out process (I ⁇ ) according to the invention when using carboxylic anhydrides can also be varied within a relatively large range. It is in general carried out at temperatures between -20° C. and +150° C., preferably between 0° C. and 100° C.
  • the starting materials of the formulae (I-1-a) to (I-8-a) and the carboxylic anhydride of the formula (XIII) are generally used in approximately equivalent amounts.
  • the carboxylic anhydride in a relatively large excess (up to 5 mol). Working up is by conventional methods.
  • the general procedure is to remove diluent, excess carboxylic anhydride and the carboxylic acid which is formed, by distillation or by washing with an organic solvent or with water.
  • Process (J) comprises reacting compounds of the formulae (I-1-a) to (I-8-a), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent, with chloroformic esters or chloroformic thioesters of the formula (XIV).
  • Suitable acid-binding agents in the reaction according to process (J) according to the invention are all customary acid acceptors.
  • Preferred possibilities for use are tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and N,N-dimethyl-aniline, alkaline earth metal oxides such as magnesium oxide and calcium oxide, alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • diluents in process (J) according to the invention it is possible to use all solvents which are inert with respect to the chloroformic esters or chloroformic thioesters.
  • Preferred possibilities for use are hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ketones such as acetone and methyl isopropyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate, and strongly polar solvents such as dimethyl sulfoxide and sulfolane.
  • reaction temperatures when carrying out process (J) according to the invention can be varied within a relatively large range.
  • the reaction temperatures are in general between -20° C. and +100° C., preferably between 0° C. and 50° C.
  • Process (J) according to the invention is generally carried out under atmospheric pressure.
  • the starting materials of the formulae (I-1-a) to (I-8-a) and the corresponding chloroformic ester or chloroformic thioester of the formula (XIV) are generally used in approximately equivalent amounts. However, it is also possible to use one or other component in a relatively large excess (up to 2 mol). Working up is then by conventional methods. The general procedure is to remove precipitated salts and to concentrate the remaining reaction mixture by stripping off the diluent.
  • Process (K) comprises reacting compounds of the formulae (I-1-a) to (I-8-a), with (K ⁇ ) compounds of the formula (XV) in the presence of a diluent and if desired in the presence of an acid-binding agent, or with (K ⁇ ) carbon disulfide and then with alkyl halides of the formula (XVI).
  • Suitable diluents which are added if desired are all inert polar organic solvents, such as ethers, amides, sulfones and sulfoxides, but also halogenoalkanes.
  • dimethyl sulfoxide tetrahydrofuran, dimethylformamide or methylene chloride.
  • the enolate salt of the compounds (I-1-a) to (I-8-a) is prepared by addition of strong deprotonating agents such as, for example, sodium hydride or potassium tert-butylate, then the addition of acid-binding agents as well can be omitted.
  • strong deprotonating agents such as, for example, sodium hydride or potassium tert-butylate
  • acid-binding agents are employed, then suitable such agents are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure, preferably at atmospheric pressure.
  • Working up is by conventional methods.
  • alkali metal hydrides As bases in process (K ⁇ ) it is possible to employ all customary proton acceptors.
  • Preferred possibilities for use are alkali metal hydrides, alkali metal alcoholates, alkali metal or akaline earth metal carbonates or hydrogen carbonates, or nitrogen bases. Examples which may be mentioned are sodium hydride, sodium methanolate, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • aromatic hydrocarbons such as benzene or toluene
  • alcohols such as methanol, ethanol, isopropanol or ethylene glycol
  • nitriles such as acetonitrile
  • ethers such as tetrahydrofuran or dioxane
  • amides such as dimethylformamide
  • other polar solvents such as dimethyl sulfoxide or sulfolane.
  • the subsequent reaction with the alkyl halide of the formula (XVI) is carried out preferably at from 0° to 70° C. and, in particular, at from 20° to 50° C. In this reaction, at least the equimolar amount of alkyl halide is employed.
  • the reaction is carried out at atmospheric pressure or under elevated pressure, preferably at atmospheric pressure.
  • Process (L) comprises reacting compounds of the formulae (I-1-a) to (I-8-a) with sulfonyl chlorides of the formula (XVII), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent.
  • Suitable diluents which may be added if desired are all inert polar organic solvents, such as ethers, amides, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.
  • dimethyl sulfoxide tetrahydrofuran, dimethylformamide or methylene chloride.
  • the enolate salt of the compounds (I-1-a) to (I-8-a) is prepared by addition of strong deprotonating agents (for example sodium hydride or potassium tert-butylate), then the addition of acid-binding agents as well can be omitted.
  • strong deprotonating agents for example sodium hydride or potassium tert-butylate
  • acid-binding agents are employed, then suitable such agents are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine or triethylamine.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure, preferably at atmospheric pressure.
  • Working up is by conventional methods.
  • Process (M) comprises reacting compounds of the formulae (I-1-a) to (I-8-a) with phosphorus compounds of the formula (XVIII), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent.
  • Suitable diluents which may be added if desired are all inert, polar, organic solvents, such as ethers, amides, nitrites, carboxylic esters, sulfides, sulfones, sulfoxides, etc.
  • Suitable acid-binding agents which may be added if desired are customary inorganic or organic bases, such as hydroxides, carbonates or amines. Examples which may be given are sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure, preferably at atmospheric pressure.
  • Working up is by conventional methods of organic chemistry.
  • the purification of the end products obtained preferably takes place by crystallization, chromatographic purification or by so-called "incipient distillation", i.e. removal of the volatile constituents in vacuo.
  • Process (N) comprises reacting compounds of the formulae (I-1-a) to (I-8-a) with metal hydroxides or metal alkoxides of the formula (XIX) or amines of the formula (XX), if desired in the presence of a diluent.
  • Process (N) is generally carried out under atmospheric pressure.
  • the reaction temperatures are in general between -20° C. and 100° C., preferably between 0° C. and 50° C.
  • Process (O) comprises reacting compounds of the formulae (I-1-a) to (I-8-a) with (O ⁇ ) compounds of the formula (XXI), if desired in the presence of a diluent and if desired in the presence of a catalyst, or (O ⁇ ) with compounds of the formula (XXII), if desired in the presence of a diluent and if desired in the presence of an acid-binding agent.
  • Suitable diluents which may be added if desired are all inert organic solvents, such as ethers, amides, nitrites, sulfones or sulfoxides.
  • catalysts it is possible if desired to add catalysts in order to accelerate the reaction.
  • organotin compounds such as, for example, dibutyltin dilaurate.
  • the process is preferably carried out at atmospheric pressure.
  • Suitable diluents which may be added if desired are all inert, polar, organic solvents, such as ethers, amides, nitrites, carboxylic esters, sulfones, sulfoxides or halogenated hydrocarbons.
  • the active compounds according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnida, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development.
  • animal pests preferably arthropods and nematodes, in particular insects and arachnida, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the abovementioned pests include:
  • Isopoda for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
  • Chilopoda for example, Geophilus carpophagus and Scutigera spec.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example, Lepisma saccharina.
  • Orthoptera for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria and Supella spp.
  • Thysanoptera From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.
  • From the order of the Homoptera for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
  • Siphonaptrida From the order of the Siphonaptrida, for example, Xenopsylla spp., Ceratophyllus spp., Pulex spp. and Ctenocephalides spp.
  • Acarina From the order of the Acarina, for example, Myocoptes spp., Otodectes spp., Acarus siro, Argas spp., Ornithodoros spp., Ornithonyssus spp., Dermanyssus spp., Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Dermacentor spp., Haemaphysalis spp., Raillietia spp.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
  • the active compounds according to the invention are distinguished by a high insecticidal and acaricidal activity.
  • the active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers.
  • weeds in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can be used, for example, in connection with the following plants:
  • the compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, ornamental plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.
  • perennial cultures for example afforestations, ornamental plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.
  • the active compounds according to the invention are very highly suited to the selective control of monocotyledon weeds in dicotyledon cultures, both pre- and post-emergence. They can, for example, be employed in cotton or sugar beet with very great success for controlling grass weeds.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine encapsulations in polymeric substances.
  • formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • solid carriers for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, ary
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations in general contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compound according to the invention may be present in its customary commercial formulations and in the use forms prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • active compounds such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the insecticides for example, include phosphates, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • dichlorophen diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,
  • fenarimol fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine,
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin,
  • pefurazoate penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB),
  • tebuconazole tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
  • bronopol dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
  • abamectin AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,
  • Bacillus thuringiensis bendiocarb, benfuracarb, bensultap, beta-cyluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,
  • fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,
  • HCH heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin,
  • parathion A parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlofos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,
  • vamidothion XMC, xylylcarb, YI 5301/5302, zetamethrin.
  • anilides such as, for example, diflufenican and propanil
  • arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram
  • aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr
  • aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl
  • azinones such as, for example, chloridazon and norflurazon
  • carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham
  • chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor
  • dinitroanilines such
  • the active compound according to the invention may also be present in its customary commercial formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents.
  • Synergistic agents are compounds which increase the activity of the active compounds without it being necessary for the synergistic agent added to be active itself.
  • the active compound content of the use forms prepared from the customary commercial formulations can vary within wide limits.
  • the active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the compounds are applied in a customary manner which is appropriate for the use forms.
  • the active compound When used against hygiene pests and pests of stored products, the active compound is distinguished by an outstanding residual action on wood and clay as well as by good stability to alkali on limed substrates.
  • the active compounds according to the invention are active not only against plant, hygiene and stored-product pests but also, in the veterinary sector, against animal parasites (ectoparasites) such as scaley ticks, argasidae, scab mites, trombidae, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. For example, they exhibit an outstanding activity against ticks such as, for example, Boophilus microplus.
  • animal parasites ectoparasites
  • ectoparasites such as scaley ticks, argasidae, scab mites, trombidae, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ticks such as, for example, Boophilus microplus.
  • the active compounds according to the invention of the formula (I) are also suitable for controlling arthropods which infest useful animals in agriculture, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets, for example, dogs, cats, cage birds, aquarium fish, and so-called experimentation animals, such as hamsters, guinea pigs, rats and mice.
  • arthropods By controlling these arthropods the intention is to reduce the occurrence of fatalities and of reductions in yield (of meat, milk, wool, skins, eggs, honey, etc.), so that the use of the active compounds according to the invention enables the keeping of animals to be more economic and more simple.
  • the active compounds according to the invention are employed in a known manner by enteral administration in the form, for example, of tablets, capsules, drinks, drenches, granules, pastes, boli, by the feed-through method, as suppositories, or by parenteral administration, for example by injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc), implants, by nasal application, by dermal application in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing, powdering and with the aid of shaped articles which contain active compound, such as collars, ear tags, tail tags, limb bands, halters, marking devices, etc.
  • enteral administration in the form, for example, of tablets, capsules, drinks, drenches, granules, pastes, boli, by the feed-through method, as suppositories
  • parenteral administration for example by injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc), implants
  • the active compounds of the formula (I) can be employed as formulations (for example powders, emulsions, flowable compositions) comprising the active compounds in a quantity of from 1 to 80% by weight, directly or after dilution by a factor of from 100 to 10,000, or they can be used as a chemical bath.
  • Example (I-2 B-a-1) Working in accordance with Example (I-2 B-a-1) and starting from the compound according to Example (III-A-2), the compound shown above is obtained as pale yellow crystals of melting point 239° C. (decomposition).
  • the compounds in the table were obtained as brown oils.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Bean plants Phaseolus vulgaris which are heavily infested by all development stages of the common spider mite or red spider mite (Tetranychus urticae) are treated by being dipped into the active compound preparation at the desired concentration.
  • the destruction is determined in %.
  • Test organisms adult sucked-up females
  • the test is carried out in 5-fold determinations. 1 ⁇ l of the solutions is injected into the abdomen, and the organisms are transferred to dishes and kept in a climate-controlled area. The activity is monitored, after 7 days, by inhibition of ovipoisition. An activity of 100% indicates that none of the ticks laid eggs.
  • the compounds according to Preparation Examples I-2 B-a-1, I-2 B-b-1 and I-2 B-c-1 showed an activity of 100% at an active compound concentration, chosen by way of example, of 20 ⁇ g/organism.

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  • Dentistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Wood Science & Technology (AREA)
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US08/836,336 1994-11-17 1995-11-06 Substituted thiophene derivatives as pesticides and herbicides Expired - Fee Related US5807805A (en)

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DE4440899 1994-11-17
DE19527190.4 1995-07-26
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DE19527190A DE19527190A1 (de) 1994-11-17 1995-07-26 Thiophenderivate
PCT/EP1995/004355 WO1996016061A1 (fr) 1994-11-17 1995-11-06 Derives de thiophene substitues utilises comme pesticides et herbicides

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US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US20030185813A1 (en) * 2000-04-14 2003-10-02 Reiner Fischer Active substance combinations with insecticidal and acaricidal properties
US20030211944A1 (en) * 2000-04-11 2003-11-13 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6653343B2 (en) 2000-02-18 2003-11-25 Bayer Aktiengesellschaft Active substance combinations comprising insecticidal and acaricidal properties
US6706758B2 (en) 2000-03-21 2004-03-16 Bayer Aktiengesellschaft Combinations of active ingredients with insecticidal and acaricidal properties
US20040161757A1 (en) * 2000-12-14 2004-08-19 Reiner Fischer Use of acetyl-coa carboxylase for identifying compounds that have an insecticidal effect
US20070222805A1 (en) * 2006-02-03 2007-09-27 Moscato Anthony V Use of a sense mark to control a printing system
US20100056620A1 (en) * 2006-06-16 2010-03-04 Bayer Cropscience Ag Active compound combinations with insecticidal and acaricidal properties

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DE10029077A1 (de) * 2000-06-13 2001-12-20 Bayer Ag Thiazolylsubstituierte Heterocyclen
DE10152005A1 (de) 2001-10-22 2003-04-30 Bayer Cropscience Ag Pyrazolylsubstituierte Heterocyclen
DE102006027732A1 (de) 2006-06-16 2008-01-10 Bayer Cropscience Ag Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften
GB0712653D0 (en) 2007-06-28 2007-08-08 Syngenta Ltd Novel herbicides
GB0714981D0 (en) 2007-08-01 2007-09-12 Syngenta Ltd Novel herbicides
GB0717082D0 (en) * 2007-09-03 2007-10-10 Syngenta Ltd Novel herbicides
US8404260B2 (en) 2008-04-02 2013-03-26 Bayer Cropscience Lp Synergistic pesticide compositions
BR112012007882B1 (pt) 2009-07-31 2017-07-25 Syngenta Limited Substituted heterarille cyclic dionas or its herbicidally active derivatives herbicide composition and method of controlling grams and seeds in plnatations
IL301822A (en) 2020-09-30 2023-06-01 Control Solutions Inc Pest control powder preparations and methods of use
MX2023010177A (es) 2021-03-01 2023-11-28 Control Solutions Inc Metodos y composiciones en particulas solidas para el control de plagas.

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US7091233B2 (en) 2000-02-18 2006-08-15 Bayer Aktiengesellschaft Active substance combinations comprising insecticidal and acaricidal properties
US20060128796A1 (en) * 2000-02-18 2006-06-15 Reiner Fischer Active substance combinations comprising insecticidal and acaricidal properties
US6653343B2 (en) 2000-02-18 2003-11-25 Bayer Aktiengesellschaft Active substance combinations comprising insecticidal and acaricidal properties
US20040044071A1 (en) * 2000-02-18 2004-03-04 Reiner Fischer Active substance combinations comprising insecticidal and acaricidal properties
US7232845B2 (en) 2000-02-18 2007-06-19 Bayer Cropscience Ag Active substance combinations comprising insecticidal and acaricidal properties
US6706758B2 (en) 2000-03-21 2004-03-16 Bayer Aktiengesellschaft Combinations of active ingredients with insecticidal and acaricidal properties
US7205289B2 (en) 2000-03-21 2007-04-17 Bayer Aktiengesellschaft Combinations of active ingredients with insecticidal and acaricidal properties
US6900190B2 (en) 2000-03-28 2005-05-31 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US7098225B2 (en) 2000-04-11 2006-08-29 Bayer Aktiengesellschaft Active compound combinations having insecticidal and acaricidal properties
US20060167085A1 (en) * 2000-04-11 2006-07-27 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US20030211944A1 (en) * 2000-04-11 2003-11-13 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6762183B2 (en) 2000-04-11 2004-07-13 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
US7244750B2 (en) 2000-04-11 2007-07-17 Bayer Cropscience Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
US20030185813A1 (en) * 2000-04-14 2003-10-02 Reiner Fischer Active substance combinations with insecticidal and acaricidal properties
US6919090B2 (en) 2000-04-14 2005-07-19 Bayer Aktiengesellschaft Active substance combinations with insecticidal and acaricidal properties
US20040161757A1 (en) * 2000-12-14 2004-08-19 Reiner Fischer Use of acetyl-coa carboxylase for identifying compounds that have an insecticidal effect
US20070222805A1 (en) * 2006-02-03 2007-09-27 Moscato Anthony V Use of a sense mark to control a printing system
US20100056620A1 (en) * 2006-06-16 2010-03-04 Bayer Cropscience Ag Active compound combinations with insecticidal and acaricidal properties

Also Published As

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AU3871095A (en) 1996-06-17
WO1996016061A1 (fr) 1996-05-30
BR9509793A (pt) 1997-09-30
EP0792272A1 (fr) 1997-09-03
US6100220A (en) 2000-08-08
JPH10509155A (ja) 1998-09-08
US6025383A (en) 2000-02-15

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